N-trityl-imidazoles as plant fungicides

ABSTRACT

WHEREIN R is alkoxy of one to three carbon atoms, sufficient to be effective for killing, combatting or controlling plant fungi, in combination with a solid or liquid diluent or carrier. Methods for killing, combatting or controlling fungal diseases in plants comprise applying to the fungi or to the plant to be protected an effective or toxic amount of the above compound.   Plant fungicidal compositions are produced which comprise an amount of a compound of the formula:

ii- United States atet [151 3,665,076 Buchel et al. 45 23, 1972N-TRITYL-IMIDAZOLES AS PLANT References Cited FUNGICIDES UNITED STATESPATENTS [721 Invent: Heinz Bum, wuppemlElberfeld; 3,321,366 5/1967Mussell et al. ..424 273 Erik Regel, Wuppertal-Cronenberg; Ferdi hand i-ewe, Burscheid lians Scheirgflgg Primary Examiner-Jerome D. GoldbergHelmut kaspe r s, both of Leverkusen, all Att0meyJacobs&Jacobs ofGermany [73] Assignee: Farbenfabriken Bayer Aktiengesellschaft, [57] CTLeverkusen, Germany Plant fungicidal compositions are produced whichcomprise [22] Filed: Sept. 2, 1970 an amount of a compound of theformula:

N 21 Appl. No.: 69,107 K J R Related US. Application Data N [62]Division of Ser. No. 789,601, Jan. 7, 1969. a s

H 30 Foreign Application Priority Data wherein R is alkoxy of 1 to 3carbon atoms, sufficient to be 1968 Germany 16 70 9765 effective forkilling, combatting or controlling plant fungi, in combination with asolid or liquid diluent or carrier. [52] U.S. Cl ..424/273 Methods forkilling, combatting or controlling fungal diseases w' 9/22 in plantscomprise applying to the fungi or to the plant to [58] Field of Search..424/273 be protected an effective or toxic amount of the abovecompound.

7 Claims, No Drawings N-TRlTYL-IMIDAZOLES AS PLANT FUNGICIDES This is adivision of our copending application, Ser. No. 789,60l,filed Jan. 7,1969.

The present invention relates to and has for its objects the provisionfor particular new l-[(halo, nitro, cyano, alkyl, alkyoxy, alkylmercaptoand fluoro-alkyl--substituted phenyl)- (bis-phenyl)-methyl]-imidazoles,i.e. certain N-tritylimidazoles, which possess fungicidal properties,active compositions in the form of mixtures of such compounds with solidand liquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating fungi, with other and further objects becoming apparent from astudy of the within specification and accompanying examples.

It is already known that N-trityl-irnidazoles of the general in which Xis an alkyl or aryl radical, and R is an aryl radical of the formula inwhich R is a halogen atom or a lower alkyl radical, and n is 0, l or 2exhibit fungitoxic properties (compare US. Pat. No. 3,321,366).

However, no N-trityl-imidazoles of the formula (i) stated above areknown in which X is always hydrogen and one of the radicals R issubstituted by R" while the two other radicals R have no substituents.

It has now been found, in accordance with the present invention, thatthe particular new N-trityl-imidazoles of the forin which R is halo,nitro, cyano, C, alkyl, C alkoxy, C alkylmercapto or fluoro-substitutedC, alkyl, exhibit strong fungicidal properties.

In our copending US. application, Ser. No. 789,602, filed Jan. 7, 1969,N-trityl-imidazolium salts, rather than N-tritylimidazoles of theinstant type, are disclosed and claimed which also possess superiorfungicidal properties.

The present invention also provides a process for the production of theN-trityl-imidazoles of the formula (I) above in which a tritylhalide ofthe formula Hal CaHruH: (Us) in which R is the same as defined above,and

Hal is a halogen atom, preferably chlorine, is reacted with imidazole(llb) in a polar inert organic solvent at a temperature of from 0 to C,in the presence of an acid binder.

The term solvent as used herein includes mere diluents It is decidedlysurprising that the specific N-trityl-imidazoles according to thepresent invention have a considerably stronger fungitoxie activity thanthe chemically very similar N- trityl-imidazoles previously known. Theactive compounds according to the present invention therefore representa valuable enrichment of the art.

The course of the reaction can be illustrated by means of the followingreaction mechanism:

Advantageously, in accordance with the present invention, in the variousformulas set forth herein:

R represents 0-, mand phalo, such as chloro, bromo, fluoro or iodo,especially chloro, bromo or fluoro, more especially o-, mand pchloro,0-, mand pfluoro, and p-bromo; or

0-, mand pnitro, especially p-nitro; or

o-, mand pcyano, especially p-cyano; or

o-, mand palkyl having one to three carbon atoms, such as methyl, ethyl,nand iso-propyl, and the like, especially oand p- C alkyl, andparticularly oand pmethyl; or

o-, mand palkoxy having one-three carbon atoms, such as methoxy, ethoxy,nand iso-propoxy, and the like, especially 0- and p- C alkoxy, andparticularly o-methoxy; or

o-, mand palkylmercapto having one-three carbon atoms such asmethylmercapto, ethylmercapto, nand iso-propylmercapto, and the like,especially oand p- C alkylmercapto, and particularly p-methylmercapto;or

o-, mand pfluoro-substituted alkyl having one-two carbon atoms such asmethyl, ethyl, and the like, especially fluoro C, alkyl having 1-5fluoro substituents, more especially mono-, diand trifluoromethyl, andmono-, di-, tri-, tetraand pentafluoroethyl, and the like, preferablym-flu0ro-C,- alkyl having l-5 fluoro groups, and particularlymtrifluoromethyl.

Preferably, R is o-, mor pchloro, bromo, fluoro, C alkyl, C alkoxy orfluoro-C alkyl having l-5 fluoro substituents.

In accordance with particular embodiments of the present invention, R ischloro, bromo, fluoro, methyl, methoxy or trifluoro methyl; or p-chloro,bromo or fluoro; or o-methyl or methoxy.

The trityl-halides required as starting materials are clearlycharacterized by the formula (Ila) above.

Some of these starting trityl-halides are known. The new startingtrityl-halides may be prepared in the same manner as the known ones.

Preparation of such starting trityl-halides may be affected as follows:first, the Grignard reagent of the mono-substituted benzene is preparedaccording to the usual methods. The mono-substituted phenylmagnesiumbromide so obtained is then reacted with benzophenone. Theorganometallic complex compound obtained is subjected to hydrolysis, theappropriate alcohol being formed [compare J. Org. Chem., 7, 392 (1942)].

From the alcohols the chlorides can be obtained simply by reaction withanhydrous hydrogen chloride or with thionyl chloride, The hydroxyl groupis replaced by chlorine [compare J. Org. Chem., 7, 392 (1942)].

Of course, the starting imidazole of formula (IIb) above is a well knowncompound.

According to the present invention, in the reaction of substitutedtrityl-halides with imidazole, polar inert organic solvents are used assolvents. These include for example, nitriles, such as acetonitrile;sulfoxides, such as dimethylsulfoxide; formamides, such as dimethylformamide; ketones, such as acetone; ethers, such as diethyl ether;nitroalkanes, such as nitromethane; unsymmetrical hydrocarbons, such aschloroform; and the like. Particularly well suited are polar inertorganic solvents which have a dielectric constant of more than 2.4.

The production reaction is carried out in the presence of anacid-binder, i. e. acid-binding agent. Preferably, a suitable excess ofimidazole is used. A tertiary amine may, however, also be added, such astriethylamine or dimethylbenzylamine. But the other organic acid-binderscustomarily employed may also be used.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the work is carried out at substantially between about 100 C,preferably between about 45 90 C.

When carrying out the production process according to the presentinvention, the starting materials are used in a molar ratio of about1:1, with about an equimolar amount of acidbinder. The reaction timesdepend on the reaction temperature and extend from about 3 to 24 hours.When working up, the solvent is removed and the reaction product isfreed from amine hydrochloride by washing with water or, if the aminehydrochloride is sparingly soluble in water, it may be separated with anorganic solvent.

Advantageously, the particular new active compounds according to thepresent invention exhibit a strong fungi-toxic activity. Because oftheir low toxicity to warm-blooded animals, they are suitable for thecontrol of undesired fungus growth. Their good compatibility with higherplants permits the use of the instant compounds as plant protectionagents against fungal plant diseases.

The instant active compounds are particularly suitable for the controlof phytopathogenic fungi on above-the-soil parts of plants, as well asagainst phytopathogenic fungi which attack the plants from the soil.

The instant active compounds exhibit a particularly high fungicidalpotency against powdery mildew fungi from the family of theErysiphaceae, for example against the fungi of the genera Frysiphe,Oidium and Podosphaera; and the like. The active compounds of thepresent invention may, however, also be used with good results for thecontrol of other phytopathogenic fungi, for example fungi which causediseases in rice and ornamental plants. The instant active compoundsshow a good activity against Piricularia oryzae, Pellicularia .vasakiiand Cochliobolus miyabeanus, three pathogenic agents which occur inrice, and against Cercospara mums; and the like. Furthermore, the growthof Phialosphora cinerescens, a fungus which attacks carnations from thesoil, is also inhibited.

The instant active compounds are distinguished by a high effectivenessin very low concentrations and by a good compatibility with plants.Doses higher than necessary for the fungicidal effect can therefore beaccepted by the plants.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withinert conventional pesticidal diluents or extenders, i.e. inertconventional pesticidal dispersible carrier vehicles, such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compoundswith conventional pesticidal dispersible liquid diluent carriers and/ordispersible solid carriers optionally with the use of carrier vehicleassistants, e.g. conventional pesticidal surface-active agents,including emulsifying agents and/or dispersing agents, whereby,forexample, in the case where water is used as diluent, organic solventsmay be added as auxiliary solvents. The following may be chieflyconsidered for use as carrier vehicles for this purpose: inertdispersible liquid diluent carriers including inert organic solvents,such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.),halo-genated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), parafiins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amines (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highlydispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereasthe following may be chiefly considered for use as conventional carriervehicle assistants, e.g. surface-active agents, for this purpose:emulsifying agents, such as non-ionic and/or anionic emulsifying agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl aryl-polyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides, orherbicides, insecticides, bactericides, etc., if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount sub-stantially between about 01-95 percent, andpreferably 0.5- percent, by weight of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.00001-2 percent,preferably 0.001-1 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (1) a dispersiblecarrier solid, and/or (2) a dispersible carrier liquid such as an inertinorganic solvent and/or water preferably including a surface-activeeffective amount of a carrier vehicle assistant, e.g. a surface-activeagent, such as an emulsifying agent and/or a dispersing agent, and anamount of the active compound which is effective for the purpose inquestion and which is generally about 0.00001- percent, and preferably0.001-95 percent, by weight of the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e. g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing l0-80 percent, preferably 20-60 percent, orgenerally from about 20 to about 95 percent by weight of the activecompound, or even the percent active substance alone, e.g. about 10-100percent by weight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling fungi, which comprises applying to atleast one of (a) such fungi and (b) their habitat, i.e. the locus to beprotected, a fungicidally effective or toxic amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring, and thelike.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration ranges.

The fungicidal effectiveness of the new compounds of the presentinvention is illustrated, without limitation, by the following examples.

EXAMPLE 1 Podosphaera Test (powdery mildew of apples) [Protective]Solvent:4.7 parts by weight acetone Emulsifier:0.3 parts by weightalkylaryl polyglycol ether Water:95.0 parts by weight The amount of theparticular active compound required for the desired concentration ofsuch active compound in the spray liquid is mixed with the stated amountof solvent, and the resulting concentrate is diluted with the statedamount of water which contains the stated emulsifier.

Young apple seedlings in the 4 6 leaf stage are sprayed (treated) withthe active compound spray liquid until dripping wet. The plants remainin a greenhouse for 24 hours at C. and at a relative atmospherichumidity of percent. The plants are then inoculated by dusting withconidia of the apple powder mildew causative organism (Podosphaeraleucotricha Salm.) and placed in a greenhouse at a temperature of 2 l-23C and at a relative atmospheric humidity of about 70 percent.

Ten days after the inoculation, the infestation of the seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

0 percent means no infestation; percent means that the infestation isexactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 1:

TABLE I.PODOSPHAERA TEST (PROTECTIVE) Infestation as a percentage of theinfestation of the untreated control with a concentration of activecompound (in percent) of- Actlveeompound 0.0062 0.0031 0.00156 Known:

(C). I N 34 55 TABLE 1.PODOSPHAERA TEST (PROTECTIVE) concentration ofnctivo compound (in percent) of- Active compound 0. 0062 0. 0031 N Cl IBr X'CZILAmQQtLZ inventioni W M fi 7 EXAMPLE 3 Active compoundscorresponding to formula (I) above in which R has the following E i h Tmeanmg: 35 Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts byweight alkylaryl polyglycol ether 1) R p- 14 34 (12) R l3 14 Water. 95.0parts by weight (31) 0 0 The amount of the particular active compoundrequired for 1) 0 l the desired concentration in the spray liquid ismixed with the 2; 5: 6 3 I 3 stated amount of the solvent, and theresulting concentrate is a 0 0 diluted with the stated amount of watercontaining the stated emulsifier. EXAMPLE 2 Young cucumber plants(Delikatess variety) with about A further test was carried out in thesame manner as Example l, with the following results:

TABLE 2 Podosphaera Test (protective) infestation as a percentage of theinfestation of the untreated control with a concentration of activecompound (in of Active Compound 0.0062 0.0031 0.00156 (-8,) R O-F 0 010 1) R 0 0 18 three foliage leaves are sprayed (treated) with theactive compound spray liquid until dripping wet. The cucumber plantsremain in a greenhouse for 24 hours to dry. The plants are then for thepurpose of inoculation, dusted with conidia of the fungus Erysiphepolyphaga. The plants are subsequently placed in a greenhouse at 2324 Cand at a relative atmospheric humidity of about percent After 12 days,the infestation of the cucumber plants is determined as a percentage ofthe untreated but also inoculated control plants. 0 percent means noinfestation; percent means that the infestation is exactly as great asin the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 3:

TABLE 3.-ERYSIPHE TEST Infestation as a percentage of the infestation ofthe untreated control with a concentration of active compound (in ofInfestation as 0. percentage of the infestation of the untreated controlwith a concentration of active compound (in of Active Compound 0. 0250.00078 0. 00019 0. 0000!) (B) 7 100 100 n 100 i 100 I Cl (C) 'l-N 43 80L l 01 I? l According to the invention 7 H Vii-7W7 I n i TABLE 4 Activecompounds corresponding to formula (1) above in which R has thefollowing Erysiphe Test meaning:

Infestation as a percentage of the 2) R PF 3) R: p l5 infestation of theuntreated i QQOUI OUI control with a concentration of active compound(in of R: m cl Active Compound 0.025 0.00078 0.000l9 0.00009 (6;) n E3;523;; g 7 R O-Cl EXAMPLE 4 EXAMPLE 5 A further test was carried out in asimilar manner as Exam- M li growth T pie 3. with the following results:Nutrient medium used:

20 parts by weight agar-agar 30 parts by weight malt extract 950 partsby weight distilled water Proportion of solvent to nutrient medium:

2 parts by weight acetone 100 parts by weight agar nutrient medium Theamount of the particular active compound required for the desiredconcentration of such active compound in the nutrient medium is mixedwith the stated amount of solvent. The resulting concentrate isthoroughly mixed, in the stated proportion, with the liquid nutrientmedium (which has been cooled to 42 C) and is then poured into Petridishes of 9 cm diameter. Control dishes to which the active compoundreparation has not been added are also set up.

When the nutrient medium has cooled and solidified, the dishes areinoculated with the species of fungi stated in the table below andincubated at about 2 l C.

Evaluation is carried out after 4-10 days, dependent upon the speed ofgrowth of the fungi. When evaluation is carried out, the radial growthof the mycelium on the treated nutrient media is compared with thegrowth on the control nutrient media. In the evaluation of the fungusgrowth, the following characteristic values are used:

no fungus growth 1 very strong inhibition of growth 2 medium inhibitionof growth 3 slight inhibition of growth 4 growth equal to that ofuntreated control.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 5:

reaction, heating at C is carried out for three hours. After cooling, 1liter of benzene is added and the reaction mixture is stirred, thenwashed salt-free with water, The benzene solution is dried overanhydrous sodium sulfate, filtered and concentrated by evaporation;giving l67 g of crude l-[ (pchlorophenyl)-(bisphenyl)-methyl]-imidazole,m.p. 125 C. By recrystallization from 200 ml benzene and 100 ml ligroin,1 15 g 71 percent of the theory) of pure l-[(p-chlorophenyl)(bis-phenyl)-methyl}-imidazole of m.p. 140 C are obtained.

EXAMPLE 7 Ti LJ 0 tHt- A) F eH 4) 34 g (0.5 mol) imidazole are dissolvedat room temperature, with stirring, in a solution of 148.25 g,(0.5 mol)of (pfluorophenyl)-(diphenyl)-methyl chloride in 500 ml acetonitrileFollowing this, 51 g (0.5 mol) triethylamine are added dropwise;triethylamine hydrochloride separates immediately upon heating. Forcompletion of the reaction, the mixture is heated at 50 C for 3 hours.After cooling, the reaction mixture is stirred together with 1 liter ofbenzene and washed salt-free with water. The benzene solution is driedover anhydrous sodium sulfate, filtered and concentrated by evaporation;giving 148 g of crude l-[(p-fluorophenyl)- (bisphenyl)-methyl]-imidazoleof m.p. 146 C 91 percent TABLE 5..\lYCELIUM GROWTH TEST FungiConcentration Phialo- C'ochiioof active Piriphora Pellu- Cerobolus 7compound cularia cinerecularz'a spore. rm'ya- Active compound in p.p.rn.oryzae scene aasukiz' muaae beamn Known:

l Cl

According to the invention:

Active compounds corresponding to formula (I) above in which R has thefollowing meaning:

(4 R =m-Cl l0 0 0 2 0 0 (52) R=p-Br l0 0 0 4 O 1 s R=m-C F; 10 0 0 3 0 0(7:) R o-Cl. 10 (l O 3 (J 0 (32) R= o-O CH; l0 0 U 2 0 0 (14) R: p-Cl Al0 0 o 4 0 0 (2;) R p-F 10 0 l 2 o o The process for producing theparticular new compounds of the present invention is illustrated,without limitation, by the following further examples:

EXAMPLE 6 of the theory). By recrystallization from 300 ml benzene and50 ml ligroin, the m.p. rises to 148 C.

The (p-fluorophenyU-(diphenyl)-methyl chloride used as starting materialcan be prepared as follows: 174.9 g (1 mol) p-fluoro-bromobenzene in mlether are slowly added dropwise to 24.3 g l gram-atom) magnesium in 300ml ether. After all the magnesium is dissolved, a solution of 182 g (1mol) benzophenone in 500 ml ether is added dropwise. The magnesium saltof the alcohol separates from the initially deep-violet solution towardsthe end of the reaction. By washing with 10 percent ammonium chloridesolution, the alcohol is obtained which, without isolation, isimmediately further processed by dissolving it in 1 liter of benzene,adding 50 g of calcium chloride and introducing hydrogen chloride gasuntil saturation. After filtration and removal of the solvent, theresulting crystal slurry is vigorously suction filtered and the crystalsobtained are washed with petroleum ether. 205

g.(=.69 percent of the theory) of (p-fluorophenyl )-(diphenyl)-methylchloride of m.p. 88 C are obtained.

EXAMPLE 8 1"! j \N maple 27.2 g (0.4 mol) imidazole and 62.8 g (0.2 mol)of (mchlorophenyl)-(diphenyl)-methyl chloride are heated to 80 C for 4hours in 150 ml of dry acetonitrile and 50 ml dimethyl formamide. Thesolvent is then drawn off and the residue is digested with water toremove the imidazole hydrochloride. The residue is taken up in methylenechloride, dried over sodium sulfate, and the viscous oil remainingbehind after the distilling off of the solvent is recrystallized fromcyclohexane. 52 g (75 percent of the theory) of l-[(m-chlorophenyl)-(bisphenyl)-methyl]-imidazole of m.p. 101 C are obtained.

In analogous manner, the following compounds of the general formula (I)above are prepared:

Compound R m.p. C.

(7 o-Cl 140 (6 m-CF 156 (3 o-OCH l30 (5 p-Br 152 (12,) p SCH 142 (lOp-CH; 130 (8:) o-F I85 (9 m-F 174 1) p-NO; 160-170 (l4,) p-CN 164 Itwill be realized by the artisan that all of the foregoing compoundscontemplated by the present invention possess the desired strongfungicidal properties, with regard to a broad spectrum of activity, aswell as a comparatively low toxicity toward warm-blooded creatures and aconcomitantly low phytotoxicity, enabling such compounds to be used withcorrespondingly favorable compatibility with warm-blooded creatures andplants for more effective control and/or elimination of fungi byapplication of such compounds to such fungi and/or their habitat.

It will be appreciated that the instant specification and examples areset forth byway of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. A method for controlling fungal diseases in plants which comprisesapplying to the fungi or to the plant to be protected a fungicidallyeffective amount of a compound of the formula:

wherein R is alkoxy of one to three carbon atoms.

2. A method according to claim 1, wherein the application is byspraying.

3. A method according to claim 1, wherein the application is byscattering the compound on the fungi or plant to be protected.

4. A method according to claim 1, wherein the application is by dustingthe compound on the fungi or plant to be protected.

5. A method according to claim 1, wherein R is methoxy.

6. A method according to claim 1, wherein R is 0- or p-alkoxy of one tothree carbon atoms.

7. A method according to claim 1, wherein R is o-methoxy.

UNITED STATES PATENT OFFICE Pag i of 5 CERTIFICATE OF CORRECTION PatentNo. 1 5.07 Dated Mav 23, 1972 n fl Karl-Heinz Buchel, Erik Regel,Ferdinand Grewe Hans Scheinpflug, Helmut Kaspers' It is certified thaterror appears in the above-identified patent Q and that said LettersPatent are hereby corrected as shown below:

In column 1, formula (i) should read )(---I IN N luv 0 3 In column 6,Table 1 should read;

TABLE l.-PODOSPHAERA 'IEST (PROTECTIVE) Infestation as a percentage ofthe infestation of the untreated control with a concentration of activecompound Lin percent) of- Active compound 0.0062 0.0031 0.00156 Known: O(A) 46 58 65 Page 2 of 5 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION PatentNo. 3,665,076 Dated May 23, 1972 Ihv n fl Karl-HeinzBuchel, Erik Regel, Ferdinand Grewe,

Hans Scheinpflug, Helmut Kaspers It is certified that error appears inthe above-identified patent Q and that said Letters Patent are herebycorrected as shown below:

Table 1 (continued) Other compounds tested g-g 34 55 o Patent: No. 3,665 ,076 Dated May Inventor(s) Karl-Heinz Buchel, Erik Regel, FerdinandGrewe,

Page 3 of 5 Hans Scheinpflug, Helmut Kaspers It is certified that errorappears in the aboveand that said Letters Patent are hereby corrected asIn column 9, Table 3 should read;

TABLE '3 -ERYSIPHE IT-ST Infestation as a percentage of the infe treatedcentration of active compound gin percent) ofidentified patent shownbelow:

station of the uncontrol with a con- Active Compound 0.025 0.000780.00019 0.00009 (B) 100 100 100 100 I (g g) Other Compounds Tested Page4 of 5 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 9 PatentNo. 3,665,076 Dated May 23, 1972 Inventor(s) Karl-Heinz Buchel, ErikRegel, Ferdinand Grewe,

Hans Scheinpflug, Helmut Kaspers It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Table 3 (continued) c1 0 43 so Q Cl 0 20 so 0 47 5 6. (yo O Page 5 of 5UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 0 Patent N6.3,665,076 Dated May 23, 1972 Inventofls) Kar I-He inz Buchel. ErikRegel, Ferdinand Grewe,

Hand Scheinpflug, Helmut Kaspers It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Add claim 8 as follows:

8. A method according to claim 1 wherein R O is methoxy, ethoxy,n-propoxy or iso-propoxy.

This certificate supersedes Certificate of Correction issued Jan. 23,1973.

. Signed and Scalzd this Second Day Of November 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner uj'lalenlsand Trademarks my UNITED s1 TES PATENT OFFICE CERTIFICATE OF CORLECTEIQN Patent No. 3, 665,076 Dated y 19,72

Inventor(s) Karl-Heinz Buchel, Erik Regel, Ferdinand Grewe,

Hans Scheinpflug Helmut Kaspers A It: is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

F Column 14, following line 37, add claim 8 as follows:

8. Amethod according to claim 1 wherein R is methoxy,ethoxy, n-propoxyor iso-propoxy.

Signed and sealed this 23rd day of January 1973'.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. ROBERT GOTTSCHALK Commissioner of PatentsAttesfcing Officer

2. A method according to claim 1, wherein the application is byspraying.
 3. A method according to claim 1, wherein the application isby scattering the compound on the fungi or plant to be protected.
 4. Amethod according to claim 1, wherein the application is by dusting thecompound on the fungi or plant to be protected.
 5. A method according toclaim 1, wherein R is methoxy.
 6. A method according to claim 1, whereinR is o- or p-alkoxy of one to three carbon atoms.
 7. A method accordingto claim 1, wherein R is o-methoxy.